Production of new vat dyestuffs of the anthraquinone acridone series and the products



Patented Mar. 22, 1932 UNITED "STATES PATENT OFFICE FRITZ ULLMANN, F GENEVA, SWITZERLAND, ssIGNon To GENERAL NrLINE WORKS INC., on NEW YORK, N. -Y., A CORPORATION OF DELAWARE PRODUCTION OF NEWVAT nYEsTUFrs OF THE -NTE'RAQUINONE ACRIDONE SERIES AND THE PRODUCTS NO Drawing. Application filed May. 22, 1929, Serial No. 365,225, and in Germany May 31, 1926.

The present invention relates to the production of new vat dyestuffs by condensation of a chlorinated anthraquinone-l.2 acridone with aromatic acid amides, furthermore it re lates to the production of Bz-dichloro-4-aminoanthraquinone-l.2-acridone from the said new arylamide compounds.

I have found that Vat dyestufls correspond- 0 ing to the general formula i O HN I in which R stands for hydrogen or an aromatic acyl radiclewhich term is meant to comprise radicles of the' type RCO- and RSO in which R is an aromatic radicle which may be further substituted, are obtained by condensing the BZ-CllCl1lOIO4-Chl(2- roanthraquinone-l.2-acridone of the formula with aromatic acld amides VlZ. aromatic carboxylic acid amides or aromatic sulphonic acid amides, and saponifying the condensation products, if desired. The vat dyestuffs of the above given general formula in which R represents an aromatic acyl radicle are'new compounds. The said Bz-dichloro i-chloroanthraquinone-l.2-acridone is obtainable by chlorinatinganthraquinone-l.2-acridone suspended in nit robenzene by means of sulphuryl-chloride with the aid of chloroiodine as halogenating catalyst as described in Example 4 of the German Patent N 0. 258,561. By the said condensation only the chlorine atom in the 4-position of the anthraquinone nucleus is substituted by the said acid amide radicles, whereas the two chlorine atoms in the benzene nucleus do not react with the acid amides. The condensation is preferably car-' ried out in a diluting or suspending medium and in the presence of acid-fixing agentssodium acetate, also condensing catalysts, such as for, example copper or copper compounds, may be added to the reaction mixture, if de- It may sometimes be advisable when producinjg' vat dyestuffs according? to the present invention to condense the" amino compound obtai'nedby saponification of thecondensation product of Bz-dichloro l-chloroanthraquinone-l.2 acridonewith an aromatic sulphonic acid amide, With a chloride of an aromatic carboxy'li'cacid instead of condensing directly an aromatic carboxylic acid amide with;Bz-dichloro-4-chloroanthraquinon e-l.2-acridone.' This manner of working is advantageously employed in all cases in which the aromatic carboxylic acid amide gives rise to secondary reactions, as for example in case of the employment of the so amide of 1-chloroanthraquinone-2-carboxylic acid. i

The condensation products exhibit a good aflinity tothe fibre and dye cotton violet to 7 blue shades of very good fastness. Likewise the saponification product dyes cotton greenish blue shades exhibiting excellent fastness properties. i

The following examples will further illus trate how the invention is carried into practical effect, but the invention is not limited thereto.

Example 1 4 parts of Bz-dichloro-4-chloroanthraquinone-1.2-acridone are heated to boiling while stirring with 1.8 parts of p toluenesulphamide, 0.6 part of anhydrous sodium acetate, 0.05 part of copper acetate and 20 parts of nitrobenzene. The initial material dissolves, the coloration of the reactionmixture rapidly turns violet and acetic acid distills ofi. When the intensity of the coloration does not an more increase, which is the case after on y a short heating period, the reaction mixture is allowed to cool'whereby it solidifies to a crystal pul V ethyl alcohol, ltered by suction, the filter cake-washed with ethyl alcohol and the violet residueboiled up with water and a small amount of dilute hydrochloric acid. .The new vat dyestufi thus obtained forms handsome violet needles with a lustre of copper after recrystallization from dichloroben Tn order to saponify the product it is introduced in about 10 parts ofconcentrated sulphuric acid and the solution warmed to about 80 C. On pouring thesolution into water the Bz dichloro 4 aminoanthraquinone-1.2 acridone separates in the form of green blue flakes and can directly be employed for d eing after filtration and washmg it free rom sulphuric acid. The dyestuflt' gives a violet vat from which cotton is dyed violet shades turning bluewith a strong greenish tinge on exposure to the air.

Example 2 If the condensation described in Example lbe carried out with an equal amount of benzainide Bz dichloro-4-benzoylamino-anthraquinone-1.2-acridone is obtained a blue violet dyestufi' which may be purified by recrystallization from dichlorobenzene or nitrobenzene. It forms beautiful, dark, violet lustrous needles, soluble in nitrobenzene givin a blue solution and being diflicultly solub e in 'dichlorobenzene. It dissolves in concentrated sulphuric acid giving a brown redsolution from which blue violet flakes separate on the addition of water. Cotton is dyed by the said dyestufl? from a violet vat blue violet extremely fast shades.

" In order to produce Bz-dichloro-4-a'mino- The pulp is diluted with anthraquinone-1.2-acridone from the aforesaid dyestufi the latter is dissolved in 10 parts Example 3 5 parts of the Bz-dichloro-4-aminoanthraquinone-L2-acridone obtainable according to the foregoing examples are mixed'with 100 parts of nitrobenzene and the mixture heated to boiling to remove traces of water. After cooling to about 150 C. 5 partsofchloroanthraquinone-Q-carboxylic acid chloride are added to the mixture which is then heated to boiling whilestirring. The-initially blue reaction mixture soon turns claret red under strong evolution of hydrogen chloride. "After the reaction is complete the reaction mixture is diluted with benzene, the reaction product filtered oil and washed with benzene. The pure new dyestufi' is obtained in the form of violet red needles exhibiting a stron lustre ofcopper of an extremely low soluility in organic solvents, but giving a brown red solution with concentrated sulphuric acid from which violet flakes separate on the addition of water. The new dyestufii' dyes cotton from a claret red vat bordeaux red shades turning violet on exposure to the air.

What I claim is I 1. As new articles of manufacture vat dyestuffs of the anthraquinone acridone series corresponding to the generalfonnula:

in which R stands for a radicle of the type RCO and RSO in which R 15 a radicle selected fromthe group consisting of benzene and anthraquinone radicles which may be substituted by an alkyl group or halogen. v

2. Theprocess of producing Bz-dichloro- 4-aminoanthraquinone-1.2-acridone which comprises condensing Bz-dichloroi-chloroanthraquinone-1.2-acridone with an acid amide of a compound selected from the group consisting of benzene and I anthraquinone which may be substituted by an alkyl group or halogen and saponifying the condensation product. e

' 3. The process of producing Bz-dichloro- 4-aminoanthraquinone-l2-acridone which comprises condensing Bz-dichloro-l-chloroanthraquinone-l.2-acridone with p-toluenesulphamide in an organic suspendingmedium in the presence of sodium acetate and copper acetate and saponifying the condensation product by warming it in concentrated sulphuric acid.

, 4:. As a. new article of manufacture the vat 1O dyestuff of the formula:

CH3 said ,dyestufi being soluble inboilingfdichlorobenzene and boiling nitrobenzene with a violet coloration, insoluble in alcohol and ether, dissolving in concentrated sulfuric acid with a brown-red coloration which turns to orange-red on short heating, and dyeing cotton from a claret red vat equal shades turning to violet on exposure to the air and wash- 5% As a new article of manufacture the vat dyestuff of the formula:

said dyestuff being soluble in nitrobenzene with a. blue coloration and diflicultly soluble in dichlorobenzene,dissolving in concentrated sulfuric acid with a brown-red coloration from which blue violet flakes separate on the addition of water, and dyeing cotton from a. violet vat blue-violet fast shades.

In testimony whereof I have hereunto set my hand.

FRITZ ULLMANN. 

